ACS Catalysis,
Год журнала:
2023,
Номер
13(24), С. 16337 - 16343
Опубликована: Дек. 6, 2023
Hydroamination
of
terminal
alkenes
represents
a
powerful
and
well-established
way
to
introduce
nitrogenous
functionality
feedstock
chemicals.
Remote
hydroamination
reactions
are
far
less
known
represent
functionalize
unactivated
C(sp3)
centers
distal
the
site
alkene.
These
transformations
commonly
take
place
via
metal-hydride-mediated
chain
walking,
as
such,
regioselectivity
can
be
challenging.
The
remote
introduction
amides
is
particular
interest
due
their
prevalence
in
pharmaceuticals.
Herein
we
report
Rh(III)-catalyzed
hydroamidation
procedure
position
internal
alkenes,
using
dioxazolones
amidation
reagents
i-PrOH
hydride
source.
reaction
proceeds
with
high
yield
tolerates
variety
functionality.
Regioconvergent
synthesis
single
linear
amide
from
mixture
isomeric
demonstrated.
Key
development
this
was
determining
that
inorganic
bases
poison
catalyst
identifying
suitable
trialkylamine
replacement.
Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
10(14), С. 3479 - 3484
Опубликована: Янв. 1, 2023
A
visible-light
induced
radical
cyclization
of
olefinic
amides
with
easily
available
N
-sulfonylaminopyridinium
salts
towards
iminoisobenzofurans
and
benzoxazines
has
been
developed.
Organic Letters,
Год журнала:
2023,
Номер
25(9), С. 1600 - 1604
Опубликована: Фев. 28, 2023
The
photoinduced
anti-Markovnikov
hydroamination
of
olefins
typically
required
photocatalysts
with
a
high
oxidative
ability
to
initiate
the
single-electron
process.
Herein,
we
alternatively
utilize
bis(2,4,6-triisopropylphenyl)
disulfide,
an
inexpensive
reagent
relatively
low
ability,
as
photo
and
hydrogen
atom
transfer
catalyst
achieve
intramolecular
hydroamination.
mechanistic
studies
well
DFT
calculations
are
consistent
novel
process
involving
N-centered
radical
generation
through
homolysis
in
situ
formed
N-S
species
subsequent
cyclization.
An
array
diverse
nitrogen-containing
cycles
could
be
obtained.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(29), С. 20349 - 20356
Опубликована: Июль 10, 2024
Catalytic
intermolecular
olefin
hydroamination
is
an
enabling
synthetic
strategy
that
offers
direct
and
atom-economical
access
to
a
variety
of
nitrogen-containing
compounds
from
abundant
feedstocks.
However,
despite
numerous
advances
in
catalyst
design
reaction
development,
N-H
azoles
with
unactivated
olefins
remains
unsolved
problem
synthesis.
We
report
dual
phosphine
photoredox
catalytic
protocol
for
the
structurally
diverse
medicinally
relevant
olefins.
Hydroamination
proceeds
high
anti-Markovnikov
regioselectivity
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(36), С. 16316 - 16324
Опубликована: Сен. 1, 2022
We
report
here
an
efficient
and
highly
diastereoselective
intermolecular
anti-Markovnikov
hydroamination
of
unactivated
alkenes
with
aliphatic
azides
in
the
presence
silane.
The
system
tolerates
a
wide
range
operates
alkene
as
limiting
reagent.
Mechanistic
studies
suggest
radical
chain
pathway
that
involves
aminium
formation,
addition
to
HAT
from
silane
β-aminium
alkyl
radical.
use
sterically
bulky
is
proposed
contribute
excellent
diastereoselectivity
for
HAT.
Computational
analysis
uncovers
reaction
azide
activation
silyl
aminyl
formation.
ACS Catalysis,
Год журнала:
2023,
Номер
13(24), С. 16337 - 16343
Опубликована: Дек. 6, 2023
Hydroamination
of
terminal
alkenes
represents
a
powerful
and
well-established
way
to
introduce
nitrogenous
functionality
feedstock
chemicals.
Remote
hydroamination
reactions
are
far
less
known
represent
functionalize
unactivated
C(sp3)
centers
distal
the
site
alkene.
These
transformations
commonly
take
place
via
metal-hydride-mediated
chain
walking,
as
such,
regioselectivity
can
be
challenging.
The
remote
introduction
amides
is
particular
interest
due
their
prevalence
in
pharmaceuticals.
Herein
we
report
Rh(III)-catalyzed
hydroamidation
procedure
position
internal
alkenes,
using
dioxazolones
amidation
reagents
i-PrOH
hydride
source.
reaction
proceeds
with
high
yield
tolerates
variety
functionality.
Regioconvergent
synthesis
single
linear
amide
from
mixture
isomeric
demonstrated.
Key
development
this
was
determining
that
inorganic
bases
poison
catalyst
identifying
suitable
trialkylamine
replacement.
